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Authors

Teles C. Furlani 1, Peter M. Edwards 2, Tara F. Kahan 3, and Cora J. Young 1

Publication Date
五月 2nd, 2022
Abstract

Total gaseous chlorine (TClg) measurements can improve our understanding of unknown sources of Cl to the atmosphere. Existing techniques for measuring TClg have been limited to offline analysis of extracted filters and do not provide suitable temporal information on fast atmospheric process. We describe high time-resolution in-situ measurements of TClg by combusting ambient air over a heated platinum (Pt) substrate coupled to a cavity ring-down spectrometer (CRDS). The method relies on the complete decomposition of TClg to release Cl atoms that react to form HCl, for which detection by CRDS has been shown to be fast and reliable. The method was validated using custom organochlorine permeation devices (PDs) that generated gas-phase dichloromethane (DCM), 1-chlorobutane (CB), and 1,3-dichloropropene (DCP). The optimal conversion temperature and residence time through the high-temperature furnace was 825 °C and 1.5 seconds, respectively. Complete conversion was indicated by the near unity orthogonal distance regression analysis slope (±σ) of 0.996 ± 0.012, 1.048 ± 0.006, and 1.027 ± 0.061 for DCM, CB, and DCP, respectively. Breaking these strong C-Cl bonds represents a proof of concept for complete conversion of all similar or weaker bonds that characterize all other TClg. We applied this technique to both outdoor and indoor environments and found reasonable comparisons in ambient background mixing ratios with the sum of expected HCl from known Cl species. We measured the converted TClg in an indoor environment during cleaning activities and observed varying levels of TClg comparable to previous studies. The method validated here is capable of measuring in-situ TClg and has a broad range of applications to make routine TClg measurements in a variety of applications.

Department of Chemistry, York University, Toronto, Canada
Department of Chemistry, University of York, York, UK
Department of Chemistry, University of Saskatchewan, Saskatoon, Canada